US20100087060A1 - Methods of forming semiconductor structures - Google Patents
Methods of forming semiconductor structures Download PDFInfo
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- US20100087060A1 US20100087060A1 US12/632,595 US63259509A US2010087060A1 US 20100087060 A1 US20100087060 A1 US 20100087060A1 US 63259509 A US63259509 A US 63259509A US 2010087060 A1 US2010087060 A1 US 2010087060A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76843—Barrier, adhesion or liner layers formed in openings in a dielectric
- H01L21/76849—Barrier, adhesion or liner layers formed in openings in a dielectric the layer being positioned on top of the main fill metal
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76867—Barrier, adhesion or liner layers characterized by methods of formation other than PVD, CVD or deposition from a liquids
Definitions
- the present invention relates to semiconductor chip processing. More particularly, the present invention relates to electrically conductive interconnects covered with interlayer dielectrics. In particular, the present invention relates to electrically conductive interconnects having a passivation layer thereon that protects the interconnects such that the formation of oxide husks thereon is substantially eliminated.
- a substrate refers to one or more semiconductor layers or structures that include active or operable portions of semiconductor devices.
- semiconductive substrate is defined to mean any construction comprising semiconductive material including, but not limited to, bulk semiconductive material such as a semiconductive wafer, either alone or in assemblies comprising other materials thereon, and semiconductive material layers, either alone or in assemblies comprising other materials.
- substrate refers to any supporting structure including, but not limited to, the semiconductive substrates described above.
- Semiconductor chip processing technology involves miniaturizing a plurality of semiconductive devices and placing them side-by-side upon a wafer. As miniaturization technology progresses, it has become expedient to stack semiconductive devices in order to retain a small chip footprint. It is also necessary to connect stacked devices by way of formation of an interconnect corridor and by filling of the interconnect corridor with electrically conductive material, such as a tungsten stud. Metallization lines are formed that make electrical connection to the tungsten stud. These metallization lines need to be electrically isolated from semiconductive devices that are formed above an existing layer of semiconductive devices. To this end, an interlayer dielectric (ILD) such as an oxide or nitride is formed.
- ILD interlayer dielectric
- FIG. 1 is a cross-sectional view of a semiconductor structure 10 that depicts interconnects 12 within a dielectric layer 14 .
- Semiconductor structure 10 has an upper surface 16 upon which an interlayer dielectric (ILD) layer 18 has been formed.
- ILD interlayer dielectric
- the left half of FIG. 1 depicts an initial effect of formation of ILD layer 18 according to the prior art.
- Oxide husk 20 is formed either after planarization to form upper surface 16 , such as by chemical-mechanical planarization (CMP) or during the deposition of ILD layer 18 .
- CMP chemical-mechanical planarization
- oxide husk 20 forms into tungsten oxide (WO 3 ).
- FIG. 1 depicts one prior art problem. It can be seen that, due to a large stress between oxide husk 20 and interconnect 12 , oxide husk 20 has delaminated from interconnect 12 due to adhesion failure, and pushed upwardly to form a void 22 immediately above interconnect 12 . Void 22 causes planarity problems and can also lead to underetched trenches prior to metal fill.
- the delamination of oxide husk 20 is an indication of a relatively thick oxide over interconnect 12 . The thickness of oxide husk 20 can range from about 10 ⁇ to about 500 ⁇ . Oxide husk 20 needs to be removed prior to deposition of a metal line.
- void 22 causes a prominence in the ILD topology.
- the prominence can lead to underetched trenches prior to metal fill, resulting in the metal line not making sufficient electrical contact with interconnect 12 .
- the prominence caused by the formation of void 22 can be formed during ILD deposition. Additionally, the prominence formed due to void 22 could cause some imaging problems because of a departure from substantial planarity of the upper surface of the ILD.
- oxide husk 20 from upper surface 16 immediately above interconnect 12 creates significant yield problems and device failure both during device testing and in the field.
- What is needed in the art is a method of overcoming the prior art problems. What is also needed in the art is a method of forming an ILD layer without the formation of an oxide husk and the subsequent formation of a void between the top of the interconnect and the ILD layer. What is needed in the art is a method of preventing or reducing the oxidation of the upper surface of a metallic interconnect during the formation of an interlayer dielectric.
- the present invention relates to the formation of an ILD layer while preventing or reducing oxidation of the upper surface of an electrically conductive interconnect or contact. Prevention or reduction of oxidation of the upper surface of an interconnect or contact is achieved according to the present invention by passivating the exposed upper surface of the interconnect or contact prior to formation of the ILD. It is to be understood that “interconnect” and “contact” can be interchangeable in the inventive method and structures.
- a preferred embodiment of the present invention comprises providing a semiconductor structure including a dielectric layer. Following the formation of the dielectric layer, a depression is formed in the dielectric layer. The depression terminates at an electrically conductive structure therebeneath. The depression is then filled with an interconnect that is composed of an electrically conductive material, such as a refractory metal, and preferably tungsten. After filling of the depression with the interconnect, an upper surface of the interconnect and dielectric layer is formed by a method such as chemical-mechanical planarization (CMP).
- CMP chemical-mechanical planarization
- a chemical composition is reacted with at least one monolayer of the upper surface of the interconnect to form a chemical compound having a higher resistance to oxidation than the interconnect.
- the chemical composition will be a nitrogen-containing chemical compound such as ammonia, NH 3 .
- the interconnect is a refractory metal, such as tungsten
- the at least one monolayer forms a tungsten nitride-type composition or adsorbed complex.
- formation of the ILD layer may be carried out by such methods as a deposition by the decomposition of tetra ethyl ortho silicate (TEOS), or by chemical vapor deposition (CVD) of oxides, nitrides, carbides, and the like.
- TEOS tetra ethyl ortho silicate
- CVD chemical vapor deposition
- a CVD be carried out under plasma-enhanced (PE) conditions, i.e., PECVD.
- PE plasma-enhanced
- Formation of the ILD layer may be carried out in a manner that introduces materials to form the ILD layer simultaneously with the introduction of the ammonia plasma to create a passivation layer upon the upper surface of the interconnect.
- the ILD layer with substantially like materials is carried out under conditions where the ILD layer substantially absorbs the passivation layer and the passivation layer is sufficiently thick to resist substantial formation of the oxide husk.
- compositions to ammonia may be used during plasma treatment of the upper surface of the interconnect.
- nitrogen-containing compositions that are preferred for the inventive method include ammonia, diatomic nitrogen, nitrogen-containing silane, and the like.
- FIG. 1 is a cross-sectional view of a semiconductor structure comprising a dielectric layer and a metallic interconnect according to the prior art. It can be seen in FIG. 1 that two stages of processing are illustrated, whereby an oxide husk upon the interconnect expands to create a void and a substantially non-planar topology for subsequently deposited layers.
- FIG. 2 is a cross-sectional view of a semiconductor structure being manufactured according to the inventive method, where a contact corridor has been opened in a dielectric layer and a liner layer has been deposited upon the dielectric layer and within the contact corridor.
- FIG. 3 is a cross-sectional view of the semiconductor structure depicted in FIG. 2 after further processing, wherein a metal nitride layer has been formed upon the liner layer, an electrically conductive stud or interconnect has been filled into the depression, and wherein an upper surface has been created by a technique such as planarization.
- the upper surface includes both the dielectric layer and the interconnect, and wherein a passivation layer has been formed upon the upper surface.
- FIG. 4 is a cross-sectional view of the semiconductor structure depicted in FIG. 3 after further processing, wherein an ILD layer has been formed upon the upper surface according to the inventing methods such that the passivation layer has substantially protected the electrically conductive stud such that oxidation has been substantially resisted.
- FIG. 5 is a cross-sectional view of the semiconductor structure depicted in FIG. 4 after further processing, wherein a second depression has been formed into the ILD layer according to damascene technology in order to allow a metallization trench to be formed, or an upper level contact to be electrically connected to the interconnect that is beneath the ILD layer.
- the present invention relates to the formation of an ILD layer while preventing or reducing oxidation of the upper surface of an interconnect or contact stud. Prevention or reduction of oxidation of the upper surface of an interconnect is achieved according to the present invention by passivating the exposed upper surface of the interconnect prior to formation of the ILD.
- prevention or reduction of the likelihood of oxidation of upper surface 16 of interconnect 12 is accomplished during the formation of ILD layer 18 . This is carried out by an in situ passivation of upper surface 16 of interconnect 12 , immediately prior to or simultaneously with the formation of ILD layer 18 , which avoids the problems of the prior art.
- a preferred embodiment of the present invention comprises providing semiconductor structure 10 including a dielectric layer 14 .
- a depression 26 is formed in dielectric layer 14 so as to terminate at an electrically conductive structure therebeneath, such as a substrate 24 .
- Depression 26 is then filled with an interconnect 12 as seen in FIG. 3 , composed of an electrically conductive material such as a refractory metal.
- Interconnect 12 can be a tungsten stud or the like.
- upper surface 16 of interconnect 12 and upper surface 16 of dielectric layer 14 is formed by a method such as CMP as illustrated in FIG. 3 .
- a chemical composition is reacted with at least one monolayer of upper surface 16 of interconnect 12 to form a chemical compound having a higher resistance to oxidation than interconnect 12 .
- the chemical compound is provided in an amount sufficient to substantially chemically cover upper surface 16 of interconnect 12 in order to chemically protect approximately the first 1-1,000 atomic lattice layers thereof.
- the chemical compound may be a nitride form of the metal of which interconnect 12 is composed. Where ammonia, a hydrated nitrogen compound or the like is used, a chemical structure such as forms, where M represents the metal of which interconnect 12 is composed.
- the chemical compound may be, by way of non-limiting example, the nitrogen-containing chemical compound such as ammonia that has been adsorbed onto upper surface 16 of interconnect 12 sufficiently to substantially chemically cover or “blind off” substantially any chemically reactive portion of upper surface 16 of interconnect 12 during formation of ILD layer 18 .
- the nitrogen-containing chemical compound such as ammonia that has been adsorbed onto upper surface 16 of interconnect 12 sufficiently to substantially chemically cover or “blind off” substantially any chemically reactive portion of upper surface 16 of interconnect 12 during formation of ILD layer 18 .
- Use of preferred chemical compounds that are to be matched with specific materials comprising interconnect 12 can be selected by one of ordinary skill in the art using such data and equations as Langmuir's monolayer adsorption isotherm or those also taught by Brunauer, Emmett, or Teller. Of interest to selection of a particular chemical compound in connection with a preferred material for interconnect 12 , will be any one of the five types of adsorption isotherms as classified by Brunauer. 1
- a passivation layer 32 substantially protects upper surface 16 of interconnect 12 from oxidation to a degree wherein the formation of oxide husk 20 and void 22 are substantially eliminated.
- Passivation layer 32 may be achieved by formation of a chemical compound upon upper surface 16 of interconnect 12 by a chemical reaction with approximately the first 1-1,000 atomic lattice layers of interconnect 12 or it may be achieved by adsorption onto upper surface 16 of interconnect 12 according to any of the aforementioned types as taught by Brunauer.
- the chemical composition will be a nitrogen-containing chemical compound such as ammonia, NH 3 .
- interconnect 12 is a tungsten stud
- the at least one monolayer reacts to form a tungsten nitride-type composition or adsorbed complex upon the at least one monolayer.
- formation of ILD layer 18 may be carried out by various methods.
- One method is deposition by the decomposition of tetra ethyl ortho silicate (TEOS), or by CVD of oxides, nitrides, carbides, and the like.
- TEOS tetra ethyl ortho silicate
- PECVD plasma-enhanced conditions
- PECVD temperatures are used in a temperature range from about 100° C. to about 600° C.
- the processing temperature will be in a range from about 150° C. to about 500° C., more preferably from about 200° C. to about 450° C., and most preferably 300° C. to about 400° C.
- a first example is set forth below.
- semiconductor substrate 24 that may be, by way of non-limiting example, a metallization line.
- a titanium liner layer 28 or the like is formed within depression 26 .
- a titanium nitride layer 30 or the like is formed upon titanium liner layer 28 as illustrated in FIG. 3 .
- Titanium nitride layer 30 may be formed by thermal nitridation of a portion of titanium liner layer 28 , by deposition of titanium nitride thereupon, or by a combination thereof.
- Interconnect 12 is next formed within depression 26 .
- a preferred material for interconnect 12 is tungsten or the like. Tungsten or the like may be formed within depression 26 by CVD, PECVD, or by physical vapor deposition (PVD).
- Upper surface 16 may be formed by such methods as CMP or an anisotropic etchback that has an etch recipe selectivity that is substantially the same for interconnect 12 as for dielectric layer 14 .
- selectivity favors leaving dielectric layer 14 , and favors it over interconnect 12 in a range from about 1.5:1, preferably about 1.2:1, more preferably 1.1:1, and most preferably 1.05:1.
- Passivation of upper surface 16 of interconnect 12 is next carried out by placing semiconductor structure 10 within a tool such as a PECVD chamber and introducing and striking an ammonia plasma or the like therein.
- Treatment temperatures are imposed upon semiconductor structure 10 .
- the plasma treats upper surface 16 for a time treatment in a range from about 1 to about 60 seconds, preferably from about 5 to about 45 seconds, more preferably from about 20 to about 40 seconds, and most preferably for about 30 seconds.
- Formation of ILD layer 18 may be carried out in a manner that introduces materials to form ILD layer 18 simultaneously with the introduction of the ammonia plasma to create a passivation layer 32 upon upper surface 16 of interconnect 12 .
- the deposition tool may be substantially evacuated of the ammonia plasma, and dielectric precursor materials may then be introduced to the deposition tool to form ILD layer 18 .
- Other materials may be used to form passivation layer 32 besides ammonia. For example, diatomic nitrogen or a nitrogen-containing silane may be used. The specific material that may be used will depend upon the particular application.
- ILD layer 18 with substantially like materials is carried out under conditions where ILD layer 18 substantially absorbs passivation layer 32 and/or passivation layer 32 is sufficiently thick to resist substantial formation of oxide husk 20 .
- both passivation layer 32 be formed using NH 3 and ILD layer 18 be formed in a deposition by decomposition of TEOS.
- Completion of this example is carried out by the formation of second depression 34 in ILD layer 18 . Accordingly, a masking layer is patterned upon upper surface 36 of ILD layer 18 and an anisotropic etch is carried out to form second depression 34 .
- the etch recipe is selective to interconnect 12 as well as titanium liner layer 28 , titanium nitride layer 30 , and optionally to dielectric layer 14 .
- passivation layer 32 is carried out at least in part by adsorption, and where ammonia is used by way of non-limiting example, an ammonia compound and its derivatives are substantially adsorbed upon upper surface 16 of interconnect 12 .
- substantially absorbed it is meant that passivation layer 32 does not volatilize during the time required to form ILD layer 18 . This means that volatilization is prevented to an extent that passivation layer 32 resists formation of oxide husk 20 , or a portion thereof.
- passivation layer 32 sufficiently protects upper surface 16 of interconnect 12 such that during the formation of ILD layer 18 , ILD layer sufficiently adheres to upper surface 16 of interconnect 12 without causing structural failure as that experienced in the prior art.
- any component of passivation layer 32 that volatilizes during formation of ILD layer 18 will be soluble in the materials that form ILD layer 18 such that no immiscible gas bubbles form from volatilized materials of passivation layer 32 .
- Semiconductor structure 10 includes dielectric layer 14 , made of borophosphosilicate glass (BPSG). Dielectric layer 14 rests upon substrate 24 .
- substrate 24 can be an electrically conductive film that is typically used to wire semiconductive devices.
- depression 26 is formed by an anisotropic dry etch that stops on substrate 24 .
- the anisotropic dry etch may include such techniques as ion beam milling or an etch recipe that mobilizes a portion of the masking layer such that the masking layer redeposits upon the sidewalls of depression 26 while it is being formed, thereby forming a substantially anisotropic etch.
- titanium liner layer 28 is deposited upon dielectric layer 14 and substrate 24 preferably by PECVD. Titanium liner layer 28 is then partially treated in a thermal nitride environment in order to grow titanium nitride layer 30 thereupon. Although titanium nitride layer 30 is grown by thermal combination and conversion of a portion of the titanium in titanium liner layer 28 into titanium nitride layer 30 , titanium nitride layer 30 may alternatively be formed by deposition of titanium nitride by such techniques as PVD, PECVD, CVD, and the like.
- interconnect 12 is formed by deposition of tungsten into depression 26 .
- the deposition of tungsten into depression 26 in order to form interconnect 12 may be facilitated by the presence of titanium nitride layer 30 and titanium liner layer 28 .
- the presence of titanium nitride layer 30 and titanium liner layer 28 facilitate slippage of the tungsten material along the region of what will become upper surface 16 and into depression 26 so as to fill depression 26 .
- interconnect 12 Following the filling of depression 26 with tungsten or the like in order to form interconnect 12 , all tungsten that is not within depression 26 is removed by a technique such as CMP. Because CMP itself may form oxide husk 20 , upper surface 16 , particularly that portion of upper surface 16 that comprises interconnect 12 , may need to be cleaned by such techniques as an interconnect oxide etch that is selective to dielectric layer 14 and unoxidized portions of interconnect 12 .
- semiconductor structure 10 is placed within a deposition tool and an ammonia plasma is struck therein.
- the cleaning of upper surface 16 may be carried out within the same deposition tool where the ammonia plasma is struck.
- the cleaning of upper surface 16 may be carried out within a cluster tool previous to in situ transfer of semiconductor structure 10 into the deposition tool.
- the temperature of semiconductor structure 10 during this stage of the inventive method is in a range substantially the same as in the previous example.
- the treatment time to form passivation layer 32 is less than about 30 seconds.
- a preferred composition of passivation layer 32 comprises nitrogen that has been adsorbed upon upper surface 16 of interconnect 12 according to Brunauer's Type V adsorption.
- upper surface 16 of interconnect 12 is first treated in a nitrogen atmosphere at a temperature sufficient to create tungsten nitride and then under conditions sufficient to create Type V adsorption of several layers of nitrogen compounds upon the tungsten nitride.
- the overall composite thickness of passivation layer 32 is about 50 ⁇ , preferably about 20 ⁇ , more preferably about 10 ⁇ , and most preferably about 5 ⁇ .
- passivation layer 32 is carried out in situ with the formation of ILD layer 18 .
- semiconductor structure 10 within a deposition tool, is fed with a mixture of ammonia and silane or the like.
- the mixture comprises an ammonia rich feed such that initially passivation layer 32 begins to form upon upper surface 16 .
- the removal of ammonia from the mixture may be carried out incrementally.
- the elimination of ammonia from the mixture may be initiated by decreasing the ammonia portion of the mixture by a preferred percentage of the entire amount of ammonia over a period of time.
- the amount of ammonia may be decreased every five seconds by about 5%, such that after about 100 seconds, the amount of ammonia in the feed mixture is reduced to about zero.
- the amount of ammonia may be decreased every five seconds by 10%, such that after about one minute, the amount of ammonia in the feed mixture is reduced to about zero.
- the amount of ammonia may be decreased by about 25% every five seconds such that after about twenty seconds, the amount of ammonia in the feed mixture has been reduced to about zero.
- the amount of ammonia may be decreased by 50% every five seconds such that after about ten seconds, the amount of ammonia in the feed mixture is reduced to about zero. Finally, the amount of ammonia in the feed mixture may be reduced from 100% to about zero after any five-second time increment in a single step.
- processing conditions may be altered from conditions that are less likely to cause formation to oxide husk 20 to conditions that are more likely.
- processing temperatures sufficient to form passivation layer 32 may be initiated with an ammonia-rich mixture under conditions not likely to cause formation of oxide husk 20 .
- processing temperatures may be increased proportionally under conditions that are more likely to cause formation of oxide husk 20 than under conditions previously established when the amount of ammonia in the mixture is greater.
- the initial formation of some of passivation layer 32 resists the formation of oxide husk 20 .
- the processing temperature will be the same as the deposition temperature for ILD layer 18 .
- passivation layer 32 Following the formation of passivation layer 32 , upper surface 16 is covered with ILD layer 18 in situ by a method as set forth above. During the deposition of ILD layer 18 , passivation layer 32 protects upper surface 16 of interconnect 12 and prevents the formation of oxide husk 20 . As a preferred alternative embodiment of the present invention, the materials comprising passivation layer 32 may react with ILD layer 18 material without causing unwanted oxidation of upper surface 16 of interconnect 12 . In this preferred alternative embodiment, the materials comprising passivation layer 32 and ILD layer 18 will interact to form a new compound that will have a lower stress than that of oxide husk 20 .
- compositions to ammonia may be used during plasma treatment of upper surface 16 of interconnect 12 .
- nitrogen-containing compositions that are preferred for the inventive method include ammonia, diatomic nitrogen, nitrogen-containing silane, and the like.
- FIG. 4 illustrates further processing of semiconductor structure 10 as depicted in FIG. 3 .
- ILD layer 18 has been formed upon upper surface 16 of semiconductor 10 according to the inventive method.
- passivation layer 32 has prevented formation on oxide husk 20 according to an object of the invention. It can be appreciated that passivation layer 32 may form exclusively upon interconnect 12 and alternatively onto titanium liner layer 28 and titanium nitride layer 30 . This means that passivation layer 32 may not substantially form upon upper surface 16 over dielectric layer 14 due to incompatible reaction chemistry that prevents any type of reactive material to form.
- Second depression 34 is formed into ILD layer 18 by patterning and etching thereof. In a damascene process such as that illustrated in FIG. 5 , second depression 34 is formed substantially above interconnect 12 .
- Second depression 34 may be, by way of non-limiting example, a wiring trench such that metallization within second depression 34 would run in and out of the plane of FIG. 5 .
- second depression 34 may be a contact corridor such that metallization would run left to right, substantially within the plane of FIG. 5 along the upper surface 36 of ILD layer 18 and filled into second depression 34 such that a metallization line with a contact is formed, whereby the contact is in electrical communication with interconnect 12 .
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Abstract
Description
- This application is a continuation of application Ser. No. 11/841,180, filed Aug. 20, 2007, pending, which is a divisional of U.S. patent application Ser. No. 09/293,188, filed Apr. 16, 1999, now U.S. Pat. No. 7,279,414, issued Oct. 9, 2007, which application is a continuation of U.S. patent application Ser. No. 09/143,289, filed on Aug. 28, 1998, titled “PLASMA TREATMENT OF AN INTERCONNECT SURFACE DURING FORMATION OF AN INTERLAYER DIELECTRIC,” now U.S. Pat. No. 6,150,257, issued Nov. 21, 2000, the disclosure of each which documents is incorporated herein in its entirety by reference.
- The present invention relates to semiconductor chip processing. More particularly, the present invention relates to electrically conductive interconnects covered with interlayer dielectrics. In particular, the present invention relates to electrically conductive interconnects having a passivation layer thereon that protects the interconnects such that the formation of oxide husks thereon is substantially eliminated.
- In the microelectronics industry, a substrate refers to one or more semiconductor layers or structures that include active or operable portions of semiconductor devices. In the context of this document, the term “semiconductive substrate” is defined to mean any construction comprising semiconductive material including, but not limited to, bulk semiconductive material such as a semiconductive wafer, either alone or in assemblies comprising other materials thereon, and semiconductive material layers, either alone or in assemblies comprising other materials. The term “substrate” refers to any supporting structure including, but not limited to, the semiconductive substrates described above.
- Semiconductor chip processing technology involves miniaturizing a plurality of semiconductive devices and placing them side-by-side upon a wafer. As miniaturization technology progresses, it has become expedient to stack semiconductive devices in order to retain a small chip footprint. It is also necessary to connect stacked devices by way of formation of an interconnect corridor and by filling of the interconnect corridor with electrically conductive material, such as a tungsten stud. Metallization lines are formed that make electrical connection to the tungsten stud. These metallization lines need to be electrically isolated from semiconductive devices that are formed above an existing layer of semiconductive devices. To this end, an interlayer dielectric (ILD) such as an oxide or nitride is formed.
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FIG. 1 is a cross-sectional view of asemiconductor structure 10 that depictsinterconnects 12 within adielectric layer 14.Semiconductor structure 10 has anupper surface 16 upon which an interlayer dielectric (ILD)layer 18 has been formed. The left half ofFIG. 1 depicts an initial effect of formation ofILD layer 18 according to the prior art. It can be seen that the portion ofinterconnect 12 that was exposed as part ofupper surface 16 ofsemiconductor structure 10 has formed anoxide husk 20 uponinterconnect 12.Oxide husk 20 is formed either after planarization to formupper surface 16, such as by chemical-mechanical planarization (CMP) or during the deposition ofILD layer 18. Where interconnect 12 is a tungsten plug, oxide husk 20 forms into tungsten oxide (WO3). - Further processing of
semiconductor structure 10, including thermal processing, causes complications that arise in the prior art. The right half ofFIG. 1 depicts one prior art problem. It can be seen that, due to a large stress betweenoxide husk 20 and interconnect 12,oxide husk 20 has delaminated frominterconnect 12 due to adhesion failure, and pushed upwardly to form avoid 22 immediately aboveinterconnect 12.Void 22 causes planarity problems and can also lead to underetched trenches prior to metal fill. The delamination ofoxide husk 20 is an indication of a relatively thick oxide overinterconnect 12. The thickness ofoxide husk 20 can range from about 10 Å to about 500 Å. Oxide husk 20 needs to be removed prior to deposition of a metal line. The presence ofvoid 22 causes a prominence in the ILD topology. The prominence can lead to underetched trenches prior to metal fill, resulting in the metal line not making sufficient electrical contact withinterconnect 12. In addition, the prominence caused by the formation ofvoid 22 can be formed during ILD deposition. Additionally, the prominence formed due tovoid 22 could cause some imaging problems because of a departure from substantial planarity of the upper surface of the ILD. - The delamination of oxide husk 20 from
upper surface 16 immediately aboveinterconnect 12 creates significant yield problems and device failure both during device testing and in the field. - What is needed in the art is a method of overcoming the prior art problems. What is also needed in the art is a method of forming an ILD layer without the formation of an oxide husk and the subsequent formation of a void between the top of the interconnect and the ILD layer. What is needed in the art is a method of preventing or reducing the oxidation of the upper surface of a metallic interconnect during the formation of an interlayer dielectric.
- The present invention relates to the formation of an ILD layer while preventing or reducing oxidation of the upper surface of an electrically conductive interconnect or contact. Prevention or reduction of oxidation of the upper surface of an interconnect or contact is achieved according to the present invention by passivating the exposed upper surface of the interconnect or contact prior to formation of the ILD. It is to be understood that “interconnect” and “contact” can be interchangeable in the inventive method and structures.
- In order to avoid the oxidation of an upper surface of an interconnect during the formation of an ILD layer, an in situ passivation of the upper surface of the interconnect, immediately prior to or simultaneously with the formation of the ILD layer, avoids the problems of the prior art.
- A preferred embodiment of the present invention comprises providing a semiconductor structure including a dielectric layer. Following the formation of the dielectric layer, a depression is formed in the dielectric layer. The depression terminates at an electrically conductive structure therebeneath. The depression is then filled with an interconnect that is composed of an electrically conductive material, such as a refractory metal, and preferably tungsten. After filling of the depression with the interconnect, an upper surface of the interconnect and dielectric layer is formed by a method such as chemical-mechanical planarization (CMP).
- Following the formation of the upper surface, a chemical composition is reacted with at least one monolayer of the upper surface of the interconnect to form a chemical compound having a higher resistance to oxidation than the interconnect.
- Preferably, the chemical composition will be a nitrogen-containing chemical compound such as ammonia, NH3. Where the interconnect is a refractory metal, such as tungsten, the at least one monolayer forms a tungsten nitride-type composition or adsorbed complex. Following formation of the at least one monolayer upon the upper surface of the interconnect, formation of the ILD layer may be carried out by such methods as a deposition by the decomposition of tetra ethyl ortho silicate (TEOS), or by chemical vapor deposition (CVD) of oxides, nitrides, carbides, and the like.
- In order to form an ILD layer using lower processing temperatures, it is preferred that a CVD be carried out under plasma-enhanced (PE) conditions, i.e., PECVD.
- Formation of the ILD layer may be carried out in a manner that introduces materials to form the ILD layer simultaneously with the introduction of the ammonia plasma to create a passivation layer upon the upper surface of the interconnect.
- Next, formation of the ILD layer with substantially like materials is carried out under conditions where the ILD layer substantially absorbs the passivation layer and the passivation layer is sufficiently thick to resist substantial formation of the oxide husk.
- Alternative compositions to ammonia may be used during plasma treatment of the upper surface of the interconnect. For example, nitrogen-containing compositions that are preferred for the inventive method include ammonia, diatomic nitrogen, nitrogen-containing silane, and the like.
- These and other features of the present invention will become more fully apparent from the following description and appended claims, or may be learned by the practice of the invention as set forth hereinafter.
- In order to illustrate the manner in which the above-recited and other advantages of the invention are obtained, a more particular description of the invention briefly described above will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings. Understanding that these drawings depict only typical embodiments of the invention and are not therefore to be considered limiting of its scope, the invention will be described and explained with additional specificity and detail through the use of the accompanying drawings in which:
-
FIG. 1 is a cross-sectional view of a semiconductor structure comprising a dielectric layer and a metallic interconnect according to the prior art. It can be seen inFIG. 1 that two stages of processing are illustrated, whereby an oxide husk upon the interconnect expands to create a void and a substantially non-planar topology for subsequently deposited layers. -
FIG. 2 is a cross-sectional view of a semiconductor structure being manufactured according to the inventive method, where a contact corridor has been opened in a dielectric layer and a liner layer has been deposited upon the dielectric layer and within the contact corridor. -
FIG. 3 is a cross-sectional view of the semiconductor structure depicted inFIG. 2 after further processing, wherein a metal nitride layer has been formed upon the liner layer, an electrically conductive stud or interconnect has been filled into the depression, and wherein an upper surface has been created by a technique such as planarization. The upper surface includes both the dielectric layer and the interconnect, and wherein a passivation layer has been formed upon the upper surface. -
FIG. 4 is a cross-sectional view of the semiconductor structure depicted inFIG. 3 after further processing, wherein an ILD layer has been formed upon the upper surface according to the inventing methods such that the passivation layer has substantially protected the electrically conductive stud such that oxidation has been substantially resisted. -
FIG. 5 is a cross-sectional view of the semiconductor structure depicted inFIG. 4 after further processing, wherein a second depression has been formed into the ILD layer according to damascene technology in order to allow a metallization trench to be formed, or an upper level contact to be electrically connected to the interconnect that is beneath the ILD layer. - Reference will now be made to the drawings wherein like structures will be provided with like reference designations. It is to be understood that the drawings are diagrammatic and schematic representations of the embodiment of the present invention and are not drawn to scale.
- The present invention relates to the formation of an ILD layer while preventing or reducing oxidation of the upper surface of an interconnect or contact stud. Prevention or reduction of oxidation of the upper surface of an interconnect is achieved according to the present invention by passivating the exposed upper surface of the interconnect prior to formation of the ILD.
- In reference to
FIG. 2 , prevention or reduction of the likelihood of oxidation ofupper surface 16 ofinterconnect 12 is accomplished during the formation ofILD layer 18. This is carried out by an in situ passivation ofupper surface 16 ofinterconnect 12, immediately prior to or simultaneously with the formation ofILD layer 18, which avoids the problems of the prior art. - A preferred embodiment of the present invention, illustrated beginning at
FIG. 2 , comprises providingsemiconductor structure 10 including adielectric layer 14. Following the formation ofdielectric layer 14, adepression 26 is formed indielectric layer 14 so as to terminate at an electrically conductive structure therebeneath, such as asubstrate 24.Depression 26 is then filled with aninterconnect 12 as seen inFIG. 3 , composed of an electrically conductive material such as a refractory metal.Interconnect 12 can be a tungsten stud or the like. After filling ofdepression 26 with an electrically conductive material,upper surface 16 ofinterconnect 12 andupper surface 16 ofdielectric layer 14 is formed by a method such as CMP as illustrated inFIG. 3 . - Following the formation of
upper surface 16, a chemical composition is reacted with at least one monolayer ofupper surface 16 ofinterconnect 12 to form a chemical compound having a higher resistance to oxidation thaninterconnect 12. - The chemical compound is provided in an amount sufficient to substantially chemically cover
upper surface 16 ofinterconnect 12 in order to chemically protect approximately the first 1-1,000 atomic lattice layers thereof. The chemical compound may be a nitride form of the metal of whichinterconnect 12 is composed. Where ammonia, a hydrated nitrogen compound or the like is used, a chemical structure such as forms, where M represents the metal of whichinterconnect 12 is composed. - The chemical compound may be, by way of non-limiting example, the nitrogen-containing chemical compound such as ammonia that has been adsorbed onto
upper surface 16 ofinterconnect 12 sufficiently to substantially chemically cover or “blind off” substantially any chemically reactive portion ofupper surface 16 ofinterconnect 12 during formation ofILD layer 18. Use of preferred chemical compounds that are to be matched with specificmaterials comprising interconnect 12 can be selected by one of ordinary skill in the art using such data and equations as Langmuir's monolayer adsorption isotherm or those also taught by Brunauer, Emmett, or Teller. Of interest to selection of a particular chemical compound in connection with a preferred material forinterconnect 12, will be any one of the five types of adsorption isotherms as classified by Brunauer.1 1 O. Hougen et al., Chemical Process Principles 2nd Ed., Chapter 10: Adsorption. John Wiley and Sons, Inc. (1954). - It is of interest in the present invention that the formation of a
passivation layer 32, as seen inFIG. 3 , substantially protectsupper surface 16 ofinterconnect 12 from oxidation to a degree wherein the formation ofoxide husk 20 and void 22 are substantially eliminated.Passivation layer 32 may be achieved by formation of a chemical compound uponupper surface 16 ofinterconnect 12 by a chemical reaction with approximately the first 1-1,000 atomic lattice layers ofinterconnect 12 or it may be achieved by adsorption ontoupper surface 16 ofinterconnect 12 according to any of the aforementioned types as taught by Brunauer. - Preferably, the chemical composition will be a nitrogen-containing chemical compound such as ammonia, NH3. Where
interconnect 12 is a tungsten stud, the at least one monolayer reacts to form a tungsten nitride-type composition or adsorbed complex upon the at least one monolayer. Following reaction with the at least one monolayer ofupper surface 16 ofinterconnect 12, formation ofILD layer 18 may be carried out by various methods. One method is deposition by the decomposition of tetra ethyl ortho silicate (TEOS), or by CVD of oxides, nitrides, carbides, and the like. - In order to form
ILD layer 18 using lower processing temperatures, it is preferred that a CVD be carried out under plasma-enhanced conditions, i.e., PECVD. According to the inventive method, PECVD temperatures are used in a temperature range from about 100° C. to about 600° C. Preferably, the processing temperature will be in a range from about 150° C. to about 500° C., more preferably from about 200° C. to about 450° C., and most preferably 300° C. to about 400° C. - According to the present invention, a first example is set forth below. Following the formation of
dielectric layer 14, as illustrated inFIG. 2 ,depression 26 such as a contact corridor is formed therein, exposingsemiconductor substrate 24 that may be, by way of non-limiting example, a metallization line. Following the exposure ofsemiconductor substrate 24, atitanium liner layer 28 or the like is formed withindepression 26. Subsequently, atitanium nitride layer 30 or the like is formed upontitanium liner layer 28 as illustrated inFIG. 3 .Titanium nitride layer 30 may be formed by thermal nitridation of a portion oftitanium liner layer 28, by deposition of titanium nitride thereupon, or by a combination thereof. -
Interconnect 12 is next formed withindepression 26. A preferred material forinterconnect 12 is tungsten or the like. Tungsten or the like may be formed withindepression 26 by CVD, PECVD, or by physical vapor deposition (PVD). -
Upper surface 16, as seen inFIG. 3 , may be formed by such methods as CMP or an anisotropic etchback that has an etch recipe selectivity that is substantially the same forinterconnect 12 as fordielectric layer 14. By “substantially the same,” it is meant that selectivity favors leavingdielectric layer 14, and favors it overinterconnect 12 in a range from about 1.5:1, preferably about 1.2:1, more preferably 1.1:1, and most preferably 1.05:1. - Passivation of
upper surface 16 ofinterconnect 12 is next carried out by placingsemiconductor structure 10 within a tool such as a PECVD chamber and introducing and striking an ammonia plasma or the like therein. Treatment temperatures, as set forth above, are imposed uponsemiconductor structure 10. The plasma treatsupper surface 16 for a time treatment in a range from about 1 to about 60 seconds, preferably from about 5 to about 45 seconds, more preferably from about 20 to about 40 seconds, and most preferably for about 30 seconds. - Formation of
ILD layer 18, as illustrated inFIG. 4 , may be carried out in a manner that introduces materials to formILD layer 18 simultaneously with the introduction of the ammonia plasma to create apassivation layer 32 uponupper surface 16 ofinterconnect 12. Alternatively, after the formation ofpassivation layer 32 has been substantially accomplished, the deposition tool may be substantially evacuated of the ammonia plasma, and dielectric precursor materials may then be introduced to the deposition tool to formILD layer 18. Other materials may be used to formpassivation layer 32 besides ammonia. For example, diatomic nitrogen or a nitrogen-containing silane may be used. The specific material that may be used will depend upon the particular application. - Next, formation of
ILD layer 18 with substantially like materials is carried out under conditions whereILD layer 18 substantially absorbspassivation layer 32 and/orpassivation layer 32 is sufficiently thick to resist substantial formation ofoxide husk 20. In this embodiment, it is preferred by way of non-limiting example that bothpassivation layer 32 be formed using NH3 andILD layer 18 be formed in a deposition by decomposition of TEOS. Other materials, however, may be chosen. - Completion of this example is carried out by the formation of
second depression 34 inILD layer 18. Accordingly, a masking layer is patterned uponupper surface 36 ofILD layer 18 and an anisotropic etch is carried out to formsecond depression 34. The etch recipe is selective to interconnect 12 as well astitanium liner layer 28,titanium nitride layer 30, and optionally todielectric layer 14. - Where formation of
passivation layer 32 is carried out at least in part by adsorption, and where ammonia is used by way of non-limiting example, an ammonia compound and its derivatives are substantially adsorbed uponupper surface 16 ofinterconnect 12. By “substantially absorbed,” it is meant thatpassivation layer 32 does not volatilize during the time required to formILD layer 18. This means that volatilization is prevented to an extent thatpassivation layer 32 resists formation ofoxide husk 20, or a portion thereof. Of primary interest in the present invention is the achievement of an embodiment wherebypassivation layer 32 sufficiently protectsupper surface 16 ofinterconnect 12 such that during the formation ofILD layer 18, ILD layer sufficiently adheres toupper surface 16 ofinterconnect 12 without causing structural failure as that experienced in the prior art. - Additionally and preferably, any component of
passivation layer 32 that volatilizes during formation ofILD layer 18 will be soluble in the materials that formILD layer 18 such that no immiscible gas bubbles form from volatilized materials ofpassivation layer 32. - A second example of the inventive method is set forth below.
Semiconductor structure 10 includesdielectric layer 14, made of borophosphosilicate glass (BPSG).Dielectric layer 14 rests uponsubstrate 24. In this example,substrate 24 can be an electrically conductive film that is typically used to wire semiconductive devices. - Following the formation of
dielectric layer 14,depression 26 is formed by an anisotropic dry etch that stops onsubstrate 24. The anisotropic dry etch may include such techniques as ion beam milling or an etch recipe that mobilizes a portion of the masking layer such that the masking layer redeposits upon the sidewalls ofdepression 26 while it is being formed, thereby forming a substantially anisotropic etch. - Following the formation of
depression 26,titanium liner layer 28 is deposited upondielectric layer 14 andsubstrate 24 preferably by PECVD.Titanium liner layer 28 is then partially treated in a thermal nitride environment in order to growtitanium nitride layer 30 thereupon. Althoughtitanium nitride layer 30 is grown by thermal combination and conversion of a portion of the titanium intitanium liner layer 28 intotitanium nitride layer 30,titanium nitride layer 30 may alternatively be formed by deposition of titanium nitride by such techniques as PVD, PECVD, CVD, and the like. - Following the formation of
titanium nitride layer 30,interconnect 12 is formed by deposition of tungsten intodepression 26. The deposition of tungsten intodepression 26 in order to forminterconnect 12 may be facilitated by the presence oftitanium nitride layer 30 andtitanium liner layer 28. Where the formation ofinterconnect 12 is formed by force-filling of tungsten intodepression 26, the presence oftitanium nitride layer 30 andtitanium liner layer 28 facilitate slippage of the tungsten material along the region of what will becomeupper surface 16 and intodepression 26 so as to filldepression 26. - Following the filling of
depression 26 with tungsten or the like in order to forminterconnect 12, all tungsten that is not withindepression 26 is removed by a technique such as CMP. Because CMP itself may formoxide husk 20,upper surface 16, particularly that portion ofupper surface 16 that comprisesinterconnect 12, may need to be cleaned by such techniques as an interconnect oxide etch that is selective todielectric layer 14 and unoxidized portions ofinterconnect 12. - Following the cleaning of
upper surface 16,semiconductor structure 10 is placed within a deposition tool and an ammonia plasma is struck therein. Alternatively, the cleaning ofupper surface 16 may be carried out within the same deposition tool where the ammonia plasma is struck. Additionally, the cleaning ofupper surface 16 may be carried out within a cluster tool previous to in situ transfer ofsemiconductor structure 10 into the deposition tool. The temperature ofsemiconductor structure 10 during this stage of the inventive method is in a range substantially the same as in the previous example. Preferably, the treatment time to formpassivation layer 32 is less than about 30 seconds. According to this second example, a preferred composition ofpassivation layer 32 comprises nitrogen that has been adsorbed uponupper surface 16 ofinterconnect 12 according to Brunauer's Type V adsorption. As a preferred alternative embodiment,upper surface 16 ofinterconnect 12 is first treated in a nitrogen atmosphere at a temperature sufficient to create tungsten nitride and then under conditions sufficient to create Type V adsorption of several layers of nitrogen compounds upon the tungsten nitride. By several layers of nitrogen compounds, it is understood that the overall composite thickness ofpassivation layer 32 is about 50 Å, preferably about 20 Å, more preferably about 10 Å, and most preferably about 5 Å. - Another example is set forth below. Processing is carried out as set forth in previous examples. The formation of
passivation layer 32 is carried out in situ with the formation ofILD layer 18. After an optional cleaning ofupper surface 16,semiconductor structure 10, within a deposition tool, is fed with a mixture of ammonia and silane or the like. At the beginning of this step of the inventive process, the mixture comprises an ammonia rich feed such that initially passivationlayer 32 begins to form uponupper surface 16. - The removal of ammonia from the mixture may be carried out incrementally. For example, the elimination of ammonia from the mixture may be initiated by decreasing the ammonia portion of the mixture by a preferred percentage of the entire amount of ammonia over a period of time. Specifically, the amount of ammonia may be decreased every five seconds by about 5%, such that after about 100 seconds, the amount of ammonia in the feed mixture is reduced to about zero. Alternatively, the amount of ammonia may be decreased every five seconds by 10%, such that after about one minute, the amount of ammonia in the feed mixture is reduced to about zero. Alternatively, the amount of ammonia may be decreased by about 25% every five seconds such that after about twenty seconds, the amount of ammonia in the feed mixture has been reduced to about zero. Additionally, the amount of ammonia may be decreased by 50% every five seconds such that after about ten seconds, the amount of ammonia in the feed mixture is reduced to about zero. Finally, the amount of ammonia in the feed mixture may be reduced from 100% to about zero after any five-second time increment in a single step.
- As an alternative embodiment and in connection with the reduction of the amount of ammonia in the mixture, processing conditions may be altered from conditions that are less likely to cause formation to
oxide husk 20 to conditions that are more likely. For example, processing temperatures sufficient to formpassivation layer 32 may be initiated with an ammonia-rich mixture under conditions not likely to cause formation ofoxide husk 20. As the amount of ammonia in the mixture is reduced, processing temperatures may be increased proportionally under conditions that are more likely to cause formation ofoxide husk 20 than under conditions previously established when the amount of ammonia in the mixture is greater. The initial formation of some ofpassivation layer 32, however, resists the formation ofoxide husk 20. Preferably, the processing temperature will be the same as the deposition temperature forILD layer 18. - Following the formation of
passivation layer 32,upper surface 16 is covered withILD layer 18 in situ by a method as set forth above. During the deposition ofILD layer 18,passivation layer 32 protectsupper surface 16 ofinterconnect 12 and prevents the formation ofoxide husk 20. As a preferred alternative embodiment of the present invention, the materials comprisingpassivation layer 32 may react withILD layer 18 material without causing unwanted oxidation ofupper surface 16 ofinterconnect 12. In this preferred alternative embodiment, the materials comprisingpassivation layer 32 andILD layer 18 will interact to form a new compound that will have a lower stress than that ofoxide husk 20. - Alternative compositions to ammonia may be used during plasma treatment of
upper surface 16 ofinterconnect 12. For example, nitrogen-containing compositions that are preferred for the inventive method include ammonia, diatomic nitrogen, nitrogen-containing silane, and the like. -
FIG. 4 illustrates further processing ofsemiconductor structure 10 as depicted inFIG. 3 . It can be seen thatILD layer 18 has been formed uponupper surface 16 ofsemiconductor 10 according to the inventive method. The presence ofpassivation layer 32 has prevented formation onoxide husk 20 according to an object of the invention. It can be appreciated thatpassivation layer 32 may form exclusively uponinterconnect 12 and alternatively ontotitanium liner layer 28 andtitanium nitride layer 30. This means thatpassivation layer 32 may not substantially form uponupper surface 16 overdielectric layer 14 due to incompatible reaction chemistry that prevents any type of reactive material to form. - Following the formation of
ILD layer 18, further processing is carried out as illustrated inFIG. 5 .Second depression 34 is formed intoILD layer 18 by patterning and etching thereof. In a damascene process such as that illustrated inFIG. 5 ,second depression 34 is formed substantially aboveinterconnect 12.Second depression 34 may be, by way of non-limiting example, a wiring trench such that metallization withinsecond depression 34 would run in and out of the plane ofFIG. 5 . Additionally,second depression 34 may be a contact corridor such that metallization would run left to right, substantially within the plane ofFIG. 5 along theupper surface 36 ofILD layer 18 and filled intosecond depression 34 such that a metallization line with a contact is formed, whereby the contact is in electrical communication withinterconnect 12. - The present invention may be embodied in other specific forms without departing from its spirit or essential characteristics. The described embodiments are to be considered in all respects only as illustrative and not restrictive. The scope of the invention is, therefore, indicated by the appended claims and their combination in whole or in part rather than by the foregoing description. All changes that come within the meaning and range of equivalency of the claims are to be embraced within their scope.
Claims (21)
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Also Published As
Publication number | Publication date |
---|---|
US6150257A (en) | 2000-11-21 |
US7659630B2 (en) | 2010-02-09 |
US20070278695A1 (en) | 2007-12-06 |
US7279414B1 (en) | 2007-10-09 |
US7955976B2 (en) | 2011-06-07 |
US6790762B1 (en) | 2004-09-14 |
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